CN112479258B - Molybdenum disulfide-carbon hollow sphere and preparation method and application thereof - Google Patents
Molybdenum disulfide-carbon hollow sphere and preparation method and application thereof Download PDFInfo
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- CN112479258B CN112479258B CN202011501382.8A CN202011501382A CN112479258B CN 112479258 B CN112479258 B CN 112479258B CN 202011501382 A CN202011501382 A CN 202011501382A CN 112479258 B CN112479258 B CN 112479258B
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- QXDDUAGHAWNZHJ-UHFFFAOYSA-N [C].[Mo](=S)=S Chemical compound [C].[Mo](=S)=S QXDDUAGHAWNZHJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 56
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 39
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 24
- 239000011733 molybdenum Substances 0.000 claims abstract description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001291 vacuum drying Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical group 0.000 claims abstract description 10
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- 239000011593 sulfur Substances 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 11
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- 239000001103 potassium chloride Substances 0.000 claims description 11
- 235000011164 potassium chloride Nutrition 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 239000011258 core-shell material Substances 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 3
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000185 sucrose group Chemical group 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 description 21
- 239000012153 distilled water Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000002077 nanosphere Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000010431 corundum Substances 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal sulfide Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- XMYKNCNAZKMVQN-NYYWCZLTSA-N [(e)-(3-aminopyridin-2-yl)methylideneamino]thiourea Chemical compound NC(=S)N\N=C\C1=NC=CC=C1N XMYKNCNAZKMVQN-NYYWCZLTSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a molybdenum disulfide-carbon hollow sphere and a preparation method and application thereof, and belongs to the field of nano material preparation. The preparation method comprises the steps of preparing a precursor solution by taking a molybdenum source, thiourea, a carbon source and an inorganic salt template as raw materials, then carrying out vacuum drying treatment on the obtained precursor solution to obtain a core/shell intermediate product with an inorganic salt core, carrying out calcination treatment to obtain a core/shell structure product with a molybdenum disulfide outer layer, and washing to remove the inorganic salt core to obtain the molybdenum disulfide-carbon hollow sphere. The preparation method has the advantages of simple process flow, low production cost and energy consumption and easy mass production. The nano molybdenum disulfide-carbon hollow sphere prepared by the invention is hollow, takes the carbon hollow sphere as a core, takes the molybdenum disulfide nanosheets as shells, has larger specific surface area, thus having more reactive sites and excellent electrocatalytic performance and battery performance, and can be applied to the fields of energy, catalysis and the like.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a molybdenum disulfide-carbon hollow sphere and a preparation method and application thereof.
Background
Molybdenum disulfide is a typical two-dimensional transition metal sulfide, and is widely used in the fields of solid lubricants, catalysis, supercapacitors and battery energy storage due to a graphene-like layered structure. As a battery material, molybdenum disulfide has a concentration of about 670 mA.h.g -1 Is easy for lithium ions to be inserted and extracted due to its structural characteristics. In addition, the layered structure of molybdenum disulfide also imparts more active sites to it, and thus is widely used as a catalyst for hydrogen evolution reactions. However, pure molybdenum disulfide is not ideal for both applications, as a battery material,the stability of the self-body is relatively poor, and the capacity attenuation is fast; as an electrocatalyst, pure molybdenum disulfide aggregates relatively easily, which greatly reduces its own active sites. Thus, the preparation of molybdenum disulfide composite materials to enhance its electrochemical properties is a hot topic.
Among the numerous composite candidate materials, carbon materials, particularly nano hollow carbon spheres, are particularly desirable to researchers. Because the nano hollow carbon sphere has a unique hollow structure and excellent physical and chemical properties, and has great application prospect in the fields of energy conversion, adsorption, biological medicine and catalysis. However, in order to obtain the hollow carbon sphere with excellent performance, the morphology and structure of the hollow carbon sphere are usually optimized and regulated. The current problems are cumbersome process, difficult to control, need to sacrifice templates and not be recoverable. Therefore, the development of the preparation method with high efficiency, no pollution and low cost has very important significance.
The invention patent CN 105098151A discloses a molybdenum disulfide-carbon hollow sphere hybrid material and a preparation method thereof. According to the method, amino modified silicon dioxide particles are used as a template, then an organic pyrolytic carbon raw material and ammonium tetrathiomolybdate are subjected to solvothermal reaction to coat the template, high-temperature treatment is carried out in an inert atmosphere, and finally the silicon dioxide template is removed, so that the molybdenum disulfide-carbon hollow sphere is obtained. Besides the complicated process and complicated preparation process, the method further increases the production cost by using hydrofluoric acid when removing the silicon dioxide, and the silicon dioxide cannot be recycled. The invention patent CN 108091837A discloses a molybdenum disulfide/carbon composite material, a preparation method and application thereof. According to the method, carbon hollow spheres with different layers are prepared by adjusting the amounts of 3-AP, formaldehyde and ammonia water, filtering, washing, drying, grinding and calcining are carried out after the hollow spheres are prepared, then the hollow spheres are added into ammonium molybdate and thiourea solution for heating reaction, and finally filtering, washing and drying are carried out. The prepared product is applied to the field of lithium ion batteries. Although the number of layers of carbon is effectively controlled, the process is complicated, and especially the reagent used in the preparation process and the acetone used for washing belong to organic substance lines, besides environmental pollution, hazard factors are more difficult to control, and the wide application of the waste liquid is further limited by post-treatment.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a molybdenum disulfide-carbon hollow sphere, and a preparation method and application thereof. The invention provides a preparation method of a molybdenum disulfide-carbon hollow sphere, which is pollution-free, environment-friendly and simple in process.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of molybdenum disulfide-carbon hollow spheres, which comprises the following steps: uniformly dispersing a molybdenum source, a sulfur source, a carbon source and an inorganic salt template in water to obtain a precursor solution; and carrying out vacuum drying treatment on the obtained precursor solution to obtain a core/shell intermediate product with an inorganic salt core, calcining the obtained core/shell intermediate product to obtain a core/shell structure product with a molybdenum disulfide outer layer, and washing the obtained core/shell structure product with the molybdenum disulfide outer layer to remove the inorganic salt core to obtain the molybdenum disulfide-carbon hollow sphere.
Preferably, the molybdenum source is ammonium molybdate, sodium molybdate, molybdenum chloride or molybdenum nitrate, and the sulfur source is thiourea.
Preferably, the carbon source is sucrose, glucose or dopamine.
Preferably, the inorganic salt template is sodium chloride or potassium chloride.
Preferably, the mass ratio of the inorganic salt template to the carbon source is 10 (1-5).
Preferably, the dosage ratio of the molybdenum source to the sulfur source is: the mol ratio of the molybdenum element to the sulfur element is 1:2.
Preferably, the total mass of the molybdenum source and the sulfur source is 10% -100% of the total mass of the carbon source.
Preferably, the conditions of the vacuum drying are: the vacuum drying temperature is 40-80 ℃ and the vacuum drying time is 12-24 h.
Further preferably, the temperature of the vacuum drying is 70 ℃ and the time is 18 hours.
Preferably, the conditions of the calcination are: the temperature rising rate is 1-5 ℃/min, the temperature keeping temperature is 400-800 ℃ and the temperature keeping time is 2-6 h under inert atmosphere.
The invention also discloses a molybdenum disulfide-carbon hollow sphere prepared by the preparation method, which comprises the following steps: taking a carbon hollow sphere as a core and taking a molybdenum disulfide nanosheet as a shell to form the molybdenum disulfide-carbon hollow sphere with a hollow core-shell structure, wherein the molybdenum disulfide-carbon hollow sphere is in a monodisperse state;
wherein the diameter of the molybdenum disulfide-carbon hollow sphere is 100-1000 nm, and the diameter of the carbon hollow sphere is 10-900 nm.
Preferably, the diameter of the molybdenum disulfide-carbon hollow sphere is 260-930 nm, and the diameter of the carbon hollow sphere is 220-900 nm.
Further preferably, the thickness of the outer shell layer of the molybdenum disulfide nanosheets is 10-70 nm.
Preferably, the molybdenum disulfide-carbon hollow sphere is 10mA cm -1 The polarization voltage corresponding to the current is 150-220 mV.
Preferably, the molybdenum disulfide-carbon hollow sphere takes 0.01-3.0V as a charge-discharge voltage range, and the specific capacity after 40 circles of electrochemical charge-discharge circulation is 620-713 mA.h/g.
The invention also discloses application of the molybdenum disulfide-carbon hollow sphere as a hydrogen evolution catalyst.
The invention also discloses application of the molybdenum disulfide-carbon hollow sphere in preparing a lithium battery anode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of molybdenum disulfide-carbon hollow spheres, which adopts the principle that the sol-gel method is adopted: during vacuum drying, an inorganic salt template in the precursor solution is separated out along with the reduction of water, so that an inorganic salt core is formed first, and along with the continuous reduction of water, a molybdenum source, a sulfur source and a carbon source are gathered on the surface of the inorganic salt core to form a shell, so that a core/shell intermediate product with the inorganic salt core is formed; the molybdenum element and the sulfur element in the molybdenum source and the sulfur source continuously form a molybdenum disulfide outer layer through high-temperature calcination treatment, so that a core/shell structure product with the molybdenum disulfide outer layer is formed; and washing to remove the inorganic salt core contained in the hollow molybdenum disulfide-carbon hollow sphere. In addition, the inorganic salt template is used as a template sacrificial agent, and can be continuously recycled through drying precipitation after being washed and removed, so that the waste of production resources is avoided, and the environment-friendly and pollution-free effects are realized; compared with the prior method, the inorganic salt template is more green in selection and convenient to process. Therefore, the preparation method disclosed by the invention has the characteristics of simple process flow, convenience in operation, no need of using an organic solvent, low production cost and energy consumption, easiness in large-scale production and wide universality.
Further, sodium chloride or potassium chloride is used as a template sacrificial agent, and after washing with distilled water, the template sacrificial agent can be continuously recycled and reused after being dried, so that the template sacrificial agent can be continuously utilized; second, either sodium chloride or potassium chloride is chosen to be readily soluble in water, ensuring that they are completely removed during the washing process.
Sodium chloride or potassium chloride is used as a template, sucrose or organic matters are used as a carbon source, molybdenum and sulfur elements are added according to a molar ratio of 1:2, and the molybdenum disulfide-carbon hollow sphere can be obtained after high-temperature calcination and washing with distilled water.
Further, the thickness of the molybdenum disulfide outer shell layer can be controlled by controlling the dosage proportion of the carbon source and the inorganic salt template, so that the preparation method can realize the controllable adjustment of the morphology of the molybdenum disulfide-carbon hollow sphere product.
The invention also discloses the molybdenum disulfide-carbon hollow sphere prepared by the preparation method, which takes the molybdenum disulfide nanosheets as shells, can effectively reach the nanoscale particle size, and has higher specific surface area by combining the two-dimensional layered structure of the molybdenum disulfide with the hollow core-shell structure of the molybdenum disulfide-carbon hollow sphere, so that the active sites of the molybdenum disulfide are greatly enriched. In addition, the molybdenum disulfide-carbon hollow spheres prepared by the preparation method are similar to sea urchin shapes, the core-shell structure of each molybdenum disulfide-carbon hollow sphere is obvious, aggregation does not occur, a monodisperse state is presented, and the electrochemical performance of the material can be effectively enhanced.
The invention also discloses application of the molybdenum disulfide-carbon hollow sphere as a hydrogen evolution catalyst and application of the molybdenum disulfide-carbon hollow sphere in preparation of a lithium battery anode material. Besides good battery performance, the molybdenum disulfide-carbon hollow sphere disclosed by the invention has the advantage that the electrocatalytic hydrogen evolution performance is not ignored. Correlation tests prove that the sample is 10mA cm -1 The polarization voltage corresponding to the current is 150-220 mV, so that the electro-catalytic hydrogen evolution performance is excellent; the specific capacity of the lithium ion battery is 620-713 mA.h/g after 40 circles of electrochemical charge-discharge cycles by taking 0.01-3.0V as a charge-discharge voltage range; therefore, the molybdenum disulfide-carbon hollow sphere has excellent electrocatalytic performance and battery performance.
Drawings
FIG. 1 is an XRD pattern of a sample of molybdenum disulfide-carbon hollow spheres prepared in example 1;
FIG. 2 is a TEM image of the molybdenum disulfide-carbon hollow spheres prepared in example 2;
FIG. 3 is a TEM image of the molybdenum disulfide-carbon hollow spheres prepared in example 3;
FIG. 4 is a TEM image of the molybdenum disulfide-carbon hollow spheres prepared in example 4;
FIG. 5 is a LSV curve of catalytic hydrogen evolution for the molybdenum disulfide-carbon hollow spheres prepared in example 4;
FIG. 6 is a graph showing the cell cycle performance of the molybdenum disulfide-carbon hollow spheres prepared in example 4;
FIG. 7 is a TEM image of the molybdenum disulfide-carbon hollow spheres prepared in example 5;
FIG. 8 is a LSV curve of catalytic hydrogen evolution for the molybdenum disulfide-carbon hollow spheres prepared in example 5;
fig. 9 is a graph showing the cell cycle performance of the molybdenum disulfide-carbon hollow spheres prepared in example 5.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a molybdenum disulfide-carbon hollow sphere, which is prepared from a precursor solution prepared from a molybdenum source, a sulfur source, a carbon source and an inorganic salt template by a sol-gel method, vacuum drying and high-temperature calcination; wherein the mol ratio of the molybdenum element to the sulfur element is 1:2;
the molybdenum disulfide-carbon hollow sphere takes a carbon hollow sphere as a core, molybdenum disulfide as a shell, and presents a hollow core-shell structure.
Specifically, the molybdenum source is ammonium molybdate, sodium molybdate, molybdenum chloride or molybdenum nitrate; the sulfur source is thiourea; the carbon source is sucrose, glucose and dopamine; the inorganic salt template is sodium chloride or potassium chloride.
The invention also discloses a preparation method of the molybdenum disulfide-carbon hollow sphere, which comprises the following steps:
1) Weighing an inorganic salt template (sodium chloride or potassium chloride), a carbon source, a molybdenum source and a sulfur source, dissolving the inorganic salt template, the carbon source, the molybdenum source and the sulfur source in distilled water, and stirring to form colorless and transparent precursor solution; wherein, the molybdenum source and the sulfur source are weighed according to the mol ratio of the molybdenum element to the sulfur element of 1:2;
2) Pouring the prepared precursor solution into a corundum porcelain boat, and vacuum drying the corundum porcelain boat in a vacuum drying oven at 40-80 ℃ for 12-24 h; (formation of inorganic salt core)
3) Calcining the product obtained by vacuum drying at 400-800 ℃ under inert gas; (formation of molybdenum disulfide outer layer)
4) And washing the calcined product with distilled water (removing the inorganic salt core) to obtain the molybdenum disulfide-carbon hollow sphere.
And (3) taking the molybdenum disulfide-carbon hollow sphere prepared in the step (4) as a core, and taking the molybdenum disulfide nanosheets as shells to form the molybdenum disulfide-carbon hollow sphere with a hollow core-shell structure.
Specifically, the molybdenum disulfide-carbon hollow spheres are in a monodisperse state.
Wherein the mass ratio of the sodium chloride or the potassium chloride to the carbon source is (0.1-5) to (0.01-0.5).
Wherein the total mass of the molybdenum source and the sulfur source is 10-100% of the total mass of the carbon source.
Preferably, the vacuum drying temperature is 70 ℃ and the drying time is 18 hours.
Wherein, the conditions of calcination are: inert atmosphere, heating rate of 1-5 ℃/min, heat preservation temperature of 400-800 ℃ and heat preservation time of 2-6 h; preferably, the conditions of calcination are: argon atmosphere, heating rate of 1-5 ℃/min, heat preservation temperature of 600-800 ℃ and heat preservation time of 2-4 h.
Specifically, in the embodiment of the invention, the diameter of the obtained molybdenum disulfide-carbon hollow sphere is 100-1000 nm, and the diameter of the carbon hollow sphere is 10-500 nm; preferably, the diameter of the molybdenum disulfide-carbon hollow sphere is 260-930 nm, the diameter of the carbon hollow sphere is 220-900 nm, and the thickness of the outer shell layer of the molybdenum disulfide nanosheets is 10-70 nm.
Because the reaction conditions in the preparation method are simple and easy to control, reactants are common substances with mild performance, toxic substances such as hydrofluoric acid, organic reagents and the like are not needed in the treatment process, and the used template has recoverability, which is incomparable with a silicon dioxide template. Therefore, the preparation method provided by the invention has popularization applicability: the invention can prepare molybdenum disulfide-carbon hollow spheres and provides possibility for the design of other metal or transition metal hollow structures. The invention is described in further detail below with reference to the attached drawings and to specific embodiments:
example 1
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 2g of sucrose and 4g of sodium chloride were weighed respectively, added to 20mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 100 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing into a vacuum drying oven, and drying at 70 ℃ for 18h.
(3) And (3) placing the dried sample into a tube furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 800 ℃, and the heat preservation time is 4 hours under the argon atmosphere.
(4) And after the furnace is cooled, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
And taking the prepared sample for X-ray analysis diffraction, wherein the obtained XRD pattern is shown in figure 1, and the position of an XRD peak of the prepared sample accords with the standard peak type of molybdenum disulfide and carbon, so that the prepared sample is proved to be pure molybdenum disulfide-carbon.
Example 2
(1) 0.0736g of ammonium molybdate, 0.0634g of thiourea, 0.2g of sucrose and 2g of sodium chloride were weighed respectively, added to 20mL of distilled water and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 68.5 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing into a vacuum drying oven, and drying at 70 ℃ for 18h.
(3) And (3) placing the dried sample into a tube furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 600 ℃, and the heat preservation time is 2h under the argon atmosphere.
(4) And after the furnace is cooled, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
The TEM image of the prepared molybdenum disulfide-carbon hollow sphere sample is shown in fig. 2, and it can be seen that the prepared molybdenum disulfide-carbon hollow sphere sample shows the appearance of hollow nanospheres after calcination and heat preservation at 600 ℃ for 2 hours, the hollow nanospheres consist of carbon hollow spheres and molybdenum disulfide nanosheets at the outer layer, the average diameter is 418nm, the average size of the carbon hollow spheres at the inner part is 323nm, and the average thickness of the molybdenum disulfide nanosheets is about 48 nm.
Example 3
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 0.4g of glucose and 2g of sodium chloride were weighed respectively, added to 15mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 51.4 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing into a vacuum drying oven, and drying at 70 ℃ for 18h.
(3) And (3) placing the dried sample into a tube furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 600 ℃, and the heat preservation time is 4 hours under the argon atmosphere.
(4) And after the furnace is cooled, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
The TEM image of the prepared molybdenum disulfide-carbon hollow sphere sample is shown in fig. 3, and it can be seen that after calcination and heat preservation for 4 hours at 600 ℃, the prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere morphology, the hollow nanosphere consists of carbon hollow spheres and molybdenum disulfide nanosheets on the outer layer, the average diameter is 331nm, the average size of the carbon hollow spheres in the interior is 228nm, and the average thickness of the molybdenum disulfide nanosheets is about 52 nm.
Example 4
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 2g of sucrose and 4g of sodium chloride were weighed respectively, added to 20mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 10.3 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing into a vacuum drying oven, and drying at 70 ℃ for 18h.
(3) And (3) placing the dried sample into a tube furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 800 ℃, and the heat preservation time is 2h under the argon atmosphere.
(4) And after the furnace is cooled, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
The TEM image of the prepared molybdenum disulfide-carbon hollow sphere sample is shown in fig. 4, and it can be seen that the prepared molybdenum disulfide-carbon hollow sphere sample shows the appearance of hollow nanospheres after calcining at 800 ℃ and preserving heat for 2 hours, the hollow nanospheres consist of carbon hollow spheres and molybdenum disulfide nanosheets at the outer layer, the average diameter is 264nm, the average size of the carbon hollow spheres in the interior is 235nm, and the average thickness of the molybdenum disulfide nanosheets is about 15 nm.
The three-electrode system is adopted, a silver chloride electrode is used as a counter electrode, a platinum electrode is used as a reference electrode, the prepared molybdenum disulfide-carbon hollow sphere is used as a working electrode, 0.5mol/L potassium hydroxide is used as electrolyte, an electrochemical workstation is used for carrying out electrocatalytic hydrogen evolution test, and the obtained polarization curve is shown in figure 5. 10mA cm -1 The corresponding polarization voltage is 156mV, which indicates that the sample has better electrocatalytic performance.
A Shenzhen Xinwei battery tester is adopted to test the charge and discharge performance of the battery of the sample in the embodiment, and a constant-current charge and discharge specific capacity circulation test experiment is carried out at a current density of 100 mA.h/g, wherein the charge and discharge voltage range is 0.01-3.0V. As shown in FIG. 6, the first charge and discharge capacities of the molybdenum disulfide-carbon hollow spheres were 1060 mA.h/g and 750 mA.h/g, respectively, and the first coulomb efficiency was 70.7%, and the specific capacity after 40 cycles was kept around 703 mA.h/g. This is significantly higher than the performance of the molybdenum disulfide-carbon hollow spheres in the published patent (CN 105098151A), indicating that the molybdenum disulfide-carbon hollow spheres prepared by this method have better cell performance.
Example 5
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 0.4g of glucose and 4g of potassium chloride were weighed out respectively, added to 20mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 51.4 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing into a vacuum drying oven, and drying at 70 ℃ for 18h.
(3) And (3) placing the dried sample into a tube furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 600 ℃, and the heat preservation time is 4 hours under the argon atmosphere.
(4) And after the furnace is cooled, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
The TEM image of the prepared molybdenum disulfide-carbon hollow sphere sample is shown in fig. 7, and it can be seen that after calcination and heat preservation for 4 hours at 600 ℃, the prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere morphology, the hollow nanosphere consists of carbon hollow spheres and molybdenum disulfide nanosheets on the outer layer, the average diameter is 413nm, the average size of the carbon hollow spheres in the interior is 281nm, and the average thickness of a molybdenum disulfide shell layer is 66nm.
The three-electrode system is adopted, a silver chloride electrode is used as a counter electrode, a platinum electrode is used as a reference electrode, the prepared molybdenum disulfide-carbon hollow sphere is used as a working electrode, 0.5mol/L potassium hydroxide is used as electrolyte, an electrochemical workstation is used for carrying out electrocatalytic hydrogen evolution test, and the obtained polarization curve is shown in figure 8. 10mA cm -1 The corresponding polarization voltage is 150mV, which indicates that the sample has better electrocatalytic performance.
A Shenzhen Xinwei battery tester is adopted to test the charge and discharge performance of the battery of the sample in the embodiment, and a constant-current charge and discharge specific capacity circulation test experiment is carried out at a current density of 100 mA.h/g, wherein the charge and discharge voltage range is 0.01-3.0V. As shown in FIG. 9, the first charge and discharge capacities of the molybdenum disulfide-carbon hollow spheres were 1075 mA.h/g and 764 mA.h/g, respectively, the first coulomb efficiency was 71%, and the specific capacity after 40 cycles was kept around 713 mA.h/g. This is significantly higher than the performance of the molybdenum disulfide-carbon hollow spheres in the published patent (CN 105098151A), indicating that the molybdenum disulfide-carbon hollow spheres prepared by this method have better cell performance.
Example 6
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 2g of glucose and 20g of potassium chloride were weighed respectively, added to 50mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 10.3 percent of the total mass of the carbon source, and the mass ratio of the carbon source to the inorganic salt template is 0.01:0.1.
(2) Pouring the colorless solution into a corundum porcelain boat, placing into a vacuum drying oven, and drying at 40 ℃ for 24 hours.
(3) And (3) placing the dried sample into a tube furnace, wherein the heating rate is 1 ℃/min, the heat preservation temperature is 400 ℃, and the heat preservation time is 6 hours under the argon atmosphere.
(4) And after the furnace is cooled, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
The prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere shape, the hollow nanosphere consists of a carbon hollow sphere and an outer layer molybdenum disulfide nanosheet, the average diameter is 926nm, the average size of the inner carbon hollow sphere is 898nm, and the average thickness of a molybdenum disulfide shell layer is 14nm.
The three-electrode system is adopted, a silver chloride electrode is a counter electrode, a platinum electrode is a reference electrode, the prepared molybdenum disulfide-carbon hollow sphere is a working electrode, 0.5mol/L potassium hydroxide is an electrolyte, and an electrochemical workstation is used for carrying out electrocatalytic hydrogen evolution test. 10mA cm -1 The corresponding polarization voltage is 220mV, which indicates that the sample has better electrocatalytic performance.
A Shenzhen Xinwei battery tester is adopted to test the charge and discharge performance of the battery of the sample in the embodiment, and a constant-current charge and discharge specific capacity circulation test experiment is carried out at a current density of 100 mA.h/g, wherein the charge and discharge voltage range is 0.01-3.0V. The specific capacity after 40 test cycles is kept around 620 mA.h/g.
Example 7
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 0.2056g of glucose and 2.056g of potassium chloride were weighed out respectively, added to 20mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 100% of the total mass of the carbon source, and the mass ratio of the carbon source to the inorganic salt template is 0.5:5.
(2) Pouring the colorless solution into a corundum porcelain boat, placing into a vacuum drying oven, and drying at 80 ℃ for 12 hours.
(3) And (3) placing the dried sample into a tube furnace, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 700 ℃, and the heat preservation time is 3 hours under the argon atmosphere.
(4) And after the furnace is cooled, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
The prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere shape, the hollow nanosphere consists of a carbon hollow sphere and an outer layer molybdenum disulfide nanosheet, the average diameter is 406nm, the average size of the inner carbon hollow sphere is 382nm, and the average thickness of a molybdenum disulfide shell layer is 11nm. .
The three-electrode system is adopted, a silver chloride electrode is a counter electrode, a platinum electrode is a reference electrode, the prepared molybdenum disulfide-carbon hollow sphere is a working electrode, 0.5mol/L potassium hydroxide is an electrolyte, and an electrochemical workstation is used for carrying out electrocatalytic hydrogen evolution test. 10mA cm -1 The corresponding polarization voltage is 208mV, which indicates that the sample has better electrocatalytic performance.
A Shenzhen Xinwei battery tester is adopted to test the charge and discharge performance of the battery of the sample in the embodiment, and a constant-current charge and discharge specific capacity circulation test experiment is carried out at a current density of 100 mA.h/g, wherein the charge and discharge voltage range is 0.01-3.0V. The specific capacity after 40 test cycles is kept at about 650 mA.h/g.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (5)
1. The preparation method of the molybdenum disulfide-carbon hollow sphere is characterized by comprising the following steps: uniformly dispersing a molybdenum source, a sulfur source, a carbon source and an inorganic salt template in water to obtain a precursor solution; performing vacuum drying treatment on the obtained precursor solution to obtain a core/shell intermediate product with an inorganic salt core, performing calcination treatment on the obtained core/shell intermediate product to obtain a core/shell structure product with a molybdenum disulfide outer layer, and performing washing treatment on the obtained core/shell structure product with the molybdenum disulfide outer layer to remove the inorganic salt core to obtain the molybdenum disulfide-carbon hollow sphere;
the mass ratio of the inorganic salt template to the carbon source is 10 (1-5);
the conditions of the vacuum drying are as follows: the vacuum drying temperature is 40-80 ℃ and the vacuum drying time is 12-24 h;
the molybdenum source is ammonium molybdate, sodium molybdate, molybdenum chloride or molybdenum nitrate, and the sulfur source is thiourea;
the carbon source is sucrose, glucose or dopamine;
the inorganic salt template is sodium chloride or potassium chloride.
2. The method for preparing the molybdenum disulfide-carbon hollow sphere according to claim 1, wherein the total mass of the molybdenum source and the sulfur source is 10% -100% of the total mass of the carbon source.
3. A molybdenum disulfide-carbon hollow sphere produced by the production process according to any one of claims 1 to 2, characterized by comprising: taking a carbon hollow sphere as a core and taking a molybdenum disulfide nanosheet as a shell to form the molybdenum disulfide-carbon hollow sphere with a hollow core-shell structure, wherein the molybdenum disulfide-carbon hollow sphere is in a monodisperse state;
wherein the diameter of the molybdenum disulfide-carbon hollow sphere is 100-1000 nm, and the diameter of the carbon hollow sphere is 10-900 nm.
4. Use of a molybdenum disulfide-carbon hollow sphere as claimed in claim 3 as a hydrogen evolution catalyst.
5. Use of a molybdenum disulfide-carbon hollow sphere as defined in claim 3 for preparing a negative electrode material of a lithium battery.
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